CN105439357A - Mine acid wastewater utilization and deep purification method - Google Patents
Mine acid wastewater utilization and deep purification method Download PDFInfo
- Publication number
- CN105439357A CN105439357A CN201510996295.7A CN201510996295A CN105439357A CN 105439357 A CN105439357 A CN 105439357A CN 201510996295 A CN201510996295 A CN 201510996295A CN 105439357 A CN105439357 A CN 105439357A
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- copper
- zinc
- acid wastewater
- mine
- vulcanizing agent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a mine acid wastewater utilization and deep purification method which comprises the following steps: (1) adjusting the pH value of mine acid wastewater using a neutralizer to recover gypsum; (2) recovering iron through two-stage neutralization; (3) recovering copper and zinc through an efficient vulcanization reaction; (4) leaching the copper and zinc residue with acid and separating copper and zinc to obtain a zinc sulfate solution and copper-rich residue; recovering the vulcanizing agent; drying the zinc sulfate solution by an MVR technology to prepare zinc sulfate; and applying the vulcanizing agent to the step (3) for the efficient vulcanization reaction; and (5) performing deep treatment and reusing the effluent or discharging when the effluent reaches the standard. By adopting the method, the recovery efficiency of copper in the mine acid wastewater can reach 85% or more, and the recovery rate of zinc is 95% or over while high-purity gypsum can be produced at the same time; compared with traditional technology, the residue quantity can be reduced by 20% or over, and the utilization of the mine acid wastewater is realized; and the new technology has the advantages of efficient purification and low cost and brings remarkable economic and environmental benefits.
Description
Technical field
The present invention relates to a kind of waste water treatment process, be specifically related to a kind of acid wastewater in mine resource utilization and deep-purifying method.Be suitable for the acid waste water process of copper-sulphide ores mining and the generation of biological wet-milling processing production process.
Background technology
In copper-sulphide ores mining and biological wet-milling processing production process, the acid wastewater in mine principal feature produced is that pH value is low, species of metal ion is many, copper, zinc, iron and sulfate radical plasma concentration higher, its pH value lower than 1.6, iron ion content higher than 7g/L, sulfate concentration reaches 20g/L, copper zinc ion content is 90-300mg/L.If acidic mine waste water enters farmland, farm crop can be made to turn to be yellow, salting of soil; Enter water body, fish and other hydrobiont can be endangered, and by food chain harmful to human.
In the industry following three kinds of methods are mainly adopted to the process of acid wastewater in mine at present:
1. with the chemical precipitation method of limestone vegetation precipitation representative.Throw out mainly by adding in neutralizing agent and acid in acid waste water and various heavy metal ion, is removed finally by solid-liquid separation, discharged wastewater met the national standard by chemical precipitation method process acid wastewater in mine.Although chemical precipitation method is through development and improve ripe day by day, because its treating processes existence precipitation additive amount of medicament is large, processing cost is high, process not thorough, produce secondary pollution, valuable constituent such as cannot to reclaim at the deficiency, the further genralrlization application of restriction the method.
2. membrane separation process.Membrane separation process be with selectivity through film for separating medium, when there is the impellents such as pressure difference, concentration difference, potential difference, temperature head when film both sides, feed side compositional selecting ground through film thus be separated, purify.Additive method must be adopted when membrane separation process being used for acid waste water technique to reclaim valuable metal, ensure the acid waste water pH qualified discharge of having purified simultaneously by neutralisation, or recycle the acid waste water of having purified.In addition, because membrane separation process exists the deficiencies such as high, the easy dirt of processing costs is stifled, working pressure is large, high content acid wastewater process is unsuitable for.
3. the method process such as biological process.The method utilizes sulphate reducing bacteria by the bioreduction of alienation vitriol, is H by sulfate reduction
2s or S
2-, and then generate sulfide precipitation with metal ion in waste water, Footwall drift sulfide; Improve wastewater pH simultaneously.The advantages such as expense is low, suitability is strong, non-secondary pollution, recyclable valuable constituent that utilize the microbial method same for treating acidic mine wastewater of sulphate reducing bacteria to have, but due to pure microbial method exist little by the restriction of organism self-ability, treatable pH scope, to deficiencies such as metal ion tolerance ability, processing efficiency are low, also be unsuitable for high content acid wastewater process, therefore fail to apply.
Along with the minimizing day by day of Global Mineral amount, and the increasingly stringent of national environmental protection policy, seek that a kind of processing cost is low, suitability is strong, environmentally friendly and the acid wastewater in mine treatment process that can reclaim valuable constituent in waste water just seems particularly urgent.
Summary of the invention
The object of the present invention is to provide a kind for the treatment of process of cupric zinc-iron high density acid wastewater in mine, it can to reclaim in waste water valuable constituent and make process water environmentally friendly, can reduce again processing cost and promote suitability.
The object of the invention is to realize in the following manner.
A kind of acid wastewater in mine resource utilization and deep-purifying method, comprise the following steps:
1) after using neutralizing agent that acid wastewater in mine pH value is transferred to 2.2-2.6, solid-liquid separation obtains gypsum;
2) remove iron ion after using neutralizing agent that acid wastewater in mine pH value is transferred to 2.8-3.2, and reclaim scum;
3) solution removed after iron is added vulcanizing agent to carry out high performance vulcanization and obtain copper cadmia;
4) after copper cadmia Ore Leaching, separation obtains rich copper ashes and solution of zinc sulfate, and reclaims vulcanizing agent;
5) advanced treatment is carried out in last water outlet.
Step 1) and 2) in neutralizing agent be calcium carbonate, sodium carbonate, magnesiumcarbonate, calcium oxide, magnesium oxide.
Step 3) in mole the measuring than being 0.9 ~ 1.3:1 of vulcanizing agent and copper zinc, the reaction times is 10 ~ 30min, and temperature of reaction is 25 ~ 55 DEG C;
Step 3) in vulcanizing agent be one or more in sodium sulphite, Sodium sulfhydrate, hydrogen sulfide, Iron sulfuret.Hydrogen sulfide is obtained by above-mentioned vulcanizing agent and sulfuric acid or hydrochloric acid reaction, or is obtained by one or more chemical combination in sulphur and methyl alcohol, Sweet natural gas, hydrogen.
Step 4) the cupric sulfide cadmia that obtains adopts wet method sulfuric acid leaching, reclaims vulcanizing agent in step 3) reaction process, obtain rich copper ashes and solution of zinc sulfate simultaneously.
Step 4) in the solution of zinc sulfate that produces adopt the technique of MVR technology or multiple-effect evaporation to obtain zinc sulfate product.
Acid wastewater in mine of the present invention produces in copper-sulphide ores mining and biological wet-milling processing production process, its pH value lower than 1.6, iron ion content higher than 7g/L, sulfate concentration reaches 20g/L, copper zinc ion content is 90-300mg/L.
Main beneficial effect of the present invention:
1. the organic efficiency of copper can reach more than 85%, the rate of recovery more than 95% of zinc, simultaneously can gypsum in efficient recovery acid waste water, and reducing the quantity of slag can reach more than 20%.
2. the high performance vulcanization reaction times is short, and it is fully efficient, facility is simple, save place floor area of building, positive effect of the present invention is the leaching again of vulcanized slag by generating, achieve the efficiently concentrating of low-concentration sulfuric acid zinc and the recycle of vulcanizing agent, be conducive to the recovery of zinc sulfate, the recycle of vulcanizing agent can save running cost more than 20%.
3. rich scum achieves the lifting of iron level in slag by enrichment process, is conducive to follow-uply carrying out recycling treatment, reduces the environmental risk when stockyard is deposited.
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is a kind for the treatment of process of copper-iron-contained high-concentration acidic mine wastewater schema proposed according to the present invention.
Embodiment
The technical problem solved to make invention, technical scheme are clearly understood, accompanying drawings and embodiment are described in further detail the present invention.Embodiment described herein in order to explain the present invention, but is not intended to limit the present invention.
Embodiment 1
Sample is taken from certain auricupride and is smelted company's raffinate waste water, and acidity is 0.33mol/L, and content of copper ion is 85mg/L, and zinc ion content is 204mg/L, and total iron ion content is 8.6g/L.Process according to the following steps:
1) after using neutralizing agent acid wastewater in mine pH value to be transferred to 2.2, solid-liquid separation obtains gypsum;
2) remove iron ion after using neutralizing agent that acid wastewater in mine pH value is transferred to 3.2, and reclaim scum;
3) solution removed after iron is added vulcanizing agent to carry out high performance vulcanization and obtain copper cadmia;
4) after copper cadmia Ore Leaching, separation obtains rich copper ashes and solution of zinc sulfate, and reclaims vulcanizing agent;
5) advanced treatment is carried out in last water outlet.
Step 1) and 2) neutralizing agent be calcium carbonate.
Step 3) in mole the measure than being 1:1 of vulcanizing agent sodium sulphite and copper zinc, the reaction times is 10min, and temperature of reaction is 30 DEG C;
Step 4) the cupric sulfide cadmia that obtains adopts wet method sulfuric acid leaching, reclaims vulcanizing agent in step 3) reaction process, obtain rich copper ashes and solution of zinc sulfate simultaneously.
Step 4) in the solution of zinc sulfate that produces adopt MVR technology to obtain zinc sulfate product.
After acid wastewater in mine resource utilization and deep-purifying method process, copper recovery 85.15%, zinc recovery 95.73%, in water outlet, the index such as copper, lead, zinc, cadmium, arsenic, mercury, COD is better than emission standard in " copper, cobalt, nickel emission of industrial pollutants standard " (GB25467-2010), and part index number is better than " Drinking Water source quality standard " (CJ3020-93).
Embodiment 2
Sample is taken from certain auricupride and is smelted company raffinate waste water B/D, and acidity is 0.41mol/L, and content of copper ion is 584mg/L, and zinc ion content is 216mg/L, and total iron ion content is 8.3g/L.Process according to the following steps:
1) after using neutralizing agent acid wastewater in mine pH value to be transferred to 2.4, solid-liquid separation obtains gypsum;
2) remove iron ion after using neutralizing agent that acid wastewater in mine pH value is transferred to 3.0, and reclaim scum;
3) solution removed after iron is added vulcanizing agent to carry out high performance vulcanization and obtain copper cadmia;
4) after copper cadmia Ore Leaching, separation obtains rich copper ashes and solution of zinc sulfate, and reclaims vulcanizing agent;
5) advanced treatment is carried out in last water outlet.
Step 1) and 2) in neutralizing agent be calcium carbonate, sodium carbonate, magnesiumcarbonate, calcium oxide, magnesium oxide.
Step 3) in mole the measure than being 1.2:1 of vulcanizing agent hydrogen sulfide and copper zinc, the reaction times is 30min, and temperature of reaction is 45 DEG C;
Step 4) the cupric sulfide cadmia that obtains adopts wet method sulfuric acid leaching, reclaims vulcanizing agent in step 3) reaction process, obtain rich copper ashes and solution of zinc sulfate simultaneously.
Step 4) in the solution of zinc sulfate that produces adopt the technique of multiple-effect evaporation to obtain zinc sulfate product.
After acid wastewater in mine resource utilization and deep-purifying method process, copper recovery 86.34%, zinc recovery 97.18%, in water outlet, the index such as copper, lead, zinc, cadmium, arsenic, mercury, COD is better than emission standard in " copper, cobalt, nickel emission of industrial pollutants standard " (GB25467-2010), and part index number is better than " Drinking Water source quality standard " (CJ3020-93).
Claims (8)
1. acid wastewater in mine resource utilization and a deep-purifying method, is characterized in that, comprises the following steps:
1) after using neutralizing agent that acid wastewater in mine pH value is transferred to 2.2-2.6, solid-liquid separation obtains gypsum;
2) remove iron ion after using neutralizing agent that acid wastewater in mine pH value is transferred to 2.8-3.2, and reclaim scum;
3) solution removed after iron is added vulcanizing agent to carry out high performance vulcanization and obtain copper cadmia;
4) after copper cadmia Ore Leaching, separation obtains rich copper ashes and solution of zinc sulfate, and reclaims vulcanizing agent;
5) advanced treatment is carried out in last water outlet.
2. method according to claim 1, is characterized in that, step 1) and 2) in neutralizing agent be calcium carbonate, sodium carbonate, magnesiumcarbonate, calcium oxide, magnesium oxide.
3. method according to claim 1, is characterized in that, step 3) in mole the measuring than being 0.9 ~ 1.3:1 of vulcanizing agent and copper zinc, the reaction times is 10 ~ 30min, and temperature of reaction is 25 ~ 55 DEG C.
4. the method according to claim 1 or 3, is characterized in that, step 3) in vulcanizing agent be one or more in sodium sulphite, Sodium sulfhydrate, hydrogen sulfide, Iron sulfuret.
5. method according to claim 4, is characterized in that, step 3) in hydrogen sulfide reacted by one or more in sulphur and hydrogen, methyl alcohol, Sweet natural gas and generate.
6. method according to claim 1, is characterized in that, step 4) the cupric sulfide cadmia that obtains adopts wet method sulfuric acid leaching, reclaims vulcanizing agent in step 3) reaction process, obtain rich copper ashes and solution of zinc sulfate simultaneously.
7. the method according to claim 1 or 6, is characterized in that, step 4) in the solution of zinc sulfate that produces adopt the technique of MVR technology or multiple-effect evaporation to obtain zinc sulfate product.
8. method according to claim 1, it is characterized in that, acid wastewater in mine produces in copper-sulphide ores mining and biological wet-milling processing production process, its pH value lower than 1.6, iron ion content higher than 7g/L, sulfate concentration reaches 20g/L, copper zinc ion content is 90-300mg/L.
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Cited By (11)
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|---|---|---|---|---|
| CN108164081A (en) * | 2016-12-07 | 2018-06-15 | 北京有色金属研究总院 | A kind of lead-zinc smelting waste acid purifying treatment method |
| CN108285239A (en) * | 2018-04-11 | 2018-07-17 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of process for treating waste liquor and system |
| CN109354252A (en) * | 2018-11-27 | 2019-02-19 | 来宾华锡冶炼有限公司 | A kind of processing method of Sewage from Sulphuric Acid Plants |
| CN109650564A (en) * | 2019-01-18 | 2019-04-19 | 广州欧邦联合建材有限公司 | A kind of sour water neutralizer and preparation method thereof |
| CN110228866A (en) * | 2019-06-10 | 2019-09-13 | 赤峰中色锌业有限公司 | A kind of waste acid sewage water treatment method and equipment |
| CN111777224A (en) * | 2020-07-10 | 2020-10-16 | 紫金矿业集团股份有限公司 | Method for comprehensively utilizing multi-metal acidic wastewater of nonferrous metal mine |
| CN113769886A (en) * | 2021-09-10 | 2021-12-10 | 厦门紫金矿冶技术有限公司 | Resource utilization method of mine high-iron high-acid wastewater neutralization slag |
| CN113968610A (en) * | 2021-09-22 | 2022-01-25 | 赛恩斯环保股份有限公司 | Method for preparing biological flocculant by using biological iron-calcium slag in biological heap leaching |
| CN114635046A (en) * | 2022-03-22 | 2022-06-17 | 中南大学 | Method for reducing zinc content in iron sediment slag in zinc hydrometallurgy process |
| CN115594278A (en) * | 2022-10-12 | 2023-01-13 | 中山大学（Cn） | Process for preparing gypsum and recovering metal from acid mine wastewater |
| CN116002935A (en) * | 2023-03-27 | 2023-04-25 | 长春黄金研究院有限公司 | Comprehensive treatment method for ferrite-containing water |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164081A (en) * | 2016-12-07 | 2018-06-15 | 北京有色金属研究总院 | A kind of lead-zinc smelting waste acid purifying treatment method |
| CN108285239A (en) * | 2018-04-11 | 2018-07-17 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of process for treating waste liquor and system |
| CN109354252A (en) * | 2018-11-27 | 2019-02-19 | 来宾华锡冶炼有限公司 | A kind of processing method of Sewage from Sulphuric Acid Plants |
| CN109650564A (en) * | 2019-01-18 | 2019-04-19 | 广州欧邦联合建材有限公司 | A kind of sour water neutralizer and preparation method thereof |
| CN110228866B (en) * | 2019-06-10 | 2024-02-09 | 赤峰中色锌业有限公司 | Method and equipment for treating sewage acid and sewage |
| CN110228866A (en) * | 2019-06-10 | 2019-09-13 | 赤峰中色锌业有限公司 | A kind of waste acid sewage water treatment method and equipment |
| CN111777224A (en) * | 2020-07-10 | 2020-10-16 | 紫金矿业集团股份有限公司 | Method for comprehensively utilizing multi-metal acidic wastewater of nonferrous metal mine |
| CN113769886A (en) * | 2021-09-10 | 2021-12-10 | 厦门紫金矿冶技术有限公司 | Resource utilization method of mine high-iron high-acid wastewater neutralization slag |
| CN113968610B (en) * | 2021-09-22 | 2022-03-15 | 赛恩斯环保股份有限公司 | Method for preparing biological flocculant by using biological iron-calcium slag in biological heap leaching |
| CN113968610A (en) * | 2021-09-22 | 2022-01-25 | 赛恩斯环保股份有限公司 | Method for preparing biological flocculant by using biological iron-calcium slag in biological heap leaching |
| CN114635046A (en) * | 2022-03-22 | 2022-06-17 | 中南大学 | Method for reducing zinc content in iron sediment slag in zinc hydrometallurgy process |
| CN115594278A (en) * | 2022-10-12 | 2023-01-13 | 中山大学（Cn） | Process for preparing gypsum and recovering metal from acid mine wastewater |
| CN116002935A (en) * | 2023-03-27 | 2023-04-25 | 长春黄金研究院有限公司 | Comprehensive treatment method for ferrite-containing water |
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